Catalysis by dispersions of metal halides in molten trihalostannate (ii) and trihalogermanate (ii) salts

ABSTRACT

Dispersions of transition and other metal halides in molten tetrahydrocarbylammonium or phosphonium trihalostannate (II) and trihalogermanate (II) salts are useful as catalysts for the hydrogenation, isomerization or carbonylation of olefins and the hydrogenation of nitriles.

United States Patent [191 Parshall Aug. 27, 1974 CATALYSIS BY DISPERSIONS OF METAL HALIDES IN MOLTEN TRIHALOSTANNATE (H) AND TRIHALOGERMANATE (II) SALTS George W. Parshall, Wilmington, Del.

Assignee: E. l. du Pont de Nemours and Company, Wilmington, Del.

Filed: Dec. 30, 1971 Appl. No.1 214,376

Related US. Application Data Division of Ser. No. 92,541, Nov. 24, 1970, Pat. No. 3,657,368, Continuation-impart of Ser. No. 727,710, May 8, 1968, Pat. No. 3,565,823.

Inventor:

US. Cl 260/497 A, 260/4105, 260/4l0.6, 260/4l0.9 R, 260/413, 260/468 M, 260/469, 260/476 R, 260/483, 260/485 R, 260/485 G,

260/491, 260/514 M, 260/515 R, 260/598, 260/599, 260/601 R, 260/604 HF, 260/409, 260/497 R, 260/526 R, 260/563 R,

[51] Int. Cl. C07c 51/14, C070 45/08 [58] Field of Search... 260/604 HF, 533 A, 533 AN, 260/497 B, 497 V References Cited UNITED STATES PATENTS 3,700,706 10/1972 Butter 260/533 A X FOREIGN PATENTS OR APPLICATIONS 1,965,942 10/1970 Germany 200/533 A Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Richard D. Kelly ABSTRACT CATALYSIS BY DISPERSIONS OF METAL HALIDES IN MOLTEN TRIHALOSTANNATE (1]) AND TRIHALOGERMANATE (ll) SALTS RELATED APPLICATION This application is a division of my copending application Ser. No. 92,541, filed Nov. 24, 1970, and now US. Pat. No. 3,657,368, itself a division and continuation-in-part of my copending application Ser. No. 727,710 filed May 8, 1968, and now US. Pat. No. 3,565,823.

BACKGROUND OF THE INVENTTON A. Field of the Invention B. Description of the Prior Art The following references are of interest in connection with the invention of this application:

2 l. R. D. Cramer et al., J. Am. Chem. Soc., 85, 1691 (1963). Solutions of chloroplatinic acid and stannous chloride are effective catalysts for the hydrogenation of olefins.

2. G. C. Bond et al., J. CataL, 7, 217 (1967). Solutions of chloroplatinic acid and stannous chloride are effective catalysts for the isomerization of l-pentene to its equilibrium mixture with Z-pentenes.

3. H. van Bekkurn et al., J. Catal., 7, 292 1967). Solutions of chloroplatinic acid and stannous chloride catalyze the hydrogenation of cyclohexene and the selective hydrogenation of dienes to monoenes.

4. L. P. vant Hoff et al., J. Catal., 7, 295 (1967). Solutions of chloroplatinic acid and stannous chloride are used as catalysts for the hydrogenation of soybean oil. Methyl linoleate gives predominantly methyl oleate.

5. E. L. Jenner et al., US. Pat. No. 2,876,254 1959). The carboxymethylation of propylene gives a product mixture containing approximately equal amounts of methyl butyrate and methyl isobutyrate.

6. F. N. Jones, J. Org. Chem, 32, 1667 (1967) and US. Pat. No. 3,397,252 (1968). lnter alia, vinyl chloride is reductively coupled to yield butadiene by Sn(ll in solutions containing catalytic amounts of PtCl cesium fluoride acting as cocatalyst.

The following art may also be of interest:

7. Th. Kruck et al., Angew Chem. intemat. Edit, 8, 679 1969). The reaction of trichlorostannate salts with metal carbonyls is used to produce complexes containing the SnCl ligand. Tetraethylammonium trichlorostannate is used in one experiment although not above its melting point. i

8. Japanese Patent 7,005,255 1970). Aliphatic polyolefins will hydrogenate to monoolefins with the catalyst HPtSnCl (PR 9. W. Wilkinson, US. Pat. No. 3,501,531 (1970). Complexes prepared from mixtures of rhodium chloride and stannous chloride are used as catalystsfor the hydroformylation of olefins.

10. R. W. Adams et al., lnorg. Nucl. Chem. Letters, 4, 455 1968). A mixture of dichlorobis(triphenylphosphine)-platinum and stannous chloride is efiective as a catalyst for the hydrogenation of terminal olefins and for the hydrogenation and isomerization of dienes.

11. L. J. Kehoe et al., J. Org. Chem, 35, 2846 (1970). Solutions of chloroplatinic acid and SnCl in ketones or ethers are used to catalyze the carbonylation of terminal olefins to alkyl esters.

SUMMARY OF THE INVENTION This invention is directed to processes employing as catalysts the liquid dispersions of my above-identified copending application. These dispersions, which include molecular dispersions, consist essentially of: (A) at least 0.05 weight percent of a ch1oride-, bromideor iodide-containing salt of a metal having an atomic number of 2628, 44-46 or 76-78, and (B) a molten salt of a compound of the formula [R R R R Q]YX wherein R, R R and R, independently, contain up to 18 carbons and are alkyl, cycloalkyl, aryl, alkaryl or aralkyl; or R and R conjointly, contain 4 to 6 carbons and is alkylene; or R R R and Q conjointly is pyridinium or quinolinium; Q is nitrogen or phosphorus; Y is tin or germanium; and X is chlorine or bromine.

The dispersions can be made, for example, by mixing componentsA and B at a temperature above the melt- 5 ing point of component B, as is fully disclosed in my c'opending application. Dispersions formed and claimed in the copending application include the following:

N,N,N,N-tetraethylammonium trichlorostannatefll) containing: PtCl PdCl RuCl hydrate; RhCl hydrate;

N,N,N,N-tetraethylammonium trichlorogermanate(ll) containing: NiBr '6H O; CoCl PdCl etc.

1n the present invention, all the above-mentioned dispersions serve as catalysts in:

A. A process for the hydrogenation of olefins and nitriles and for the isomerization of olefins; and

B. A process for the carbonylation of olefins.

A. HYDROGENATTON AND ISOMERlZATlON The process for the hydrogenation of olefins or nitriles is conducted by heating a mixture of hydrogen and an olefin, including a cycloolefin, or a nitrile in the presence of a catalytically effective amount of at least one of the above-noted metal halide-trihalostannate(II) or -trihalogermanate(ll) dispersions at a temperature of at least the melting point temperature of said dispersion.

Any olefin can be hydrogenated according to the invention, but the reaction may be expressed more particularly by the equation which follows (A signifies that the temperature is high enough to keep the catalyst molten):

wherein R R, R and R individually, are hydrogen, alkyl of up to 12 carbons, alkenyl of up to 12 carbons, aryl of up to 10 carbons, aralkyl of up to 10 carbons,

= CH+CH with the proviso that at least two of R, R, R and R are hydrogen. Included within the definition of the olefin are 1,5-cyclooctadiene, l,5-cyclododecadiene and l,5,9-cyclododecatriene.

In the hydrogenation of olefins, as in all the processes of the invention, an effective catalytic amount of the disper 'ons of my above-mentioned application or mixtures t ereof is usedf ln general, an effective catalytic amount will be dependent upon the conditions, the reactants, the particular process and metal halide dispersion. Preferably, 0.005 to 10 weight percent of the metal halide in the dispersion based on the olefin reactant is used. Most preferably, 0.5 to weight percent of the metal halide in the dispersion is used.

The rates of reaction of the processes are dependent upon the temperature and the reactants used. In general, the temperature of reaction will be as low as about C. and up to 350C.

Pressure reactors may be necessary for the processes to effect reaction. In general, the pressure will be autogenous pressures to 1,500 atmospheres or higher.

The time of the reaction will vary from a very short time of a few minutes or less to a few hours or longer. Shorter reaction times are preferred since they give more economical processes.

Concomitant with the present hydrogenation of the olefins occurs an isomerization of starting material or product. The isomerization may, in fact, occur at such a low hydrogen concentration that no hydrogenation takes place, but a small (catalytic) amount of hydrogen is believed always to be present. Conditions are otherwise the same as for the hydrogenation. The isomerization of the olefins is of two types: l isomerization of a cis isomer to the trans isomer or vice versa; and (2) position isomerization such as isomerization of the olefin to a different structure. An example of the latter type of isomerization is the conversion of a a-pinene to a-terpinene, dipentene or y-terpinene.

The process of hydrogenation of nitriles, except for the nitrile reactant, employs essentially the conditions of the hydrogenation of olefins, and may be expressed by the equation:

l R -GEN 1'12 PM-JP-NH:

cat.

wherein R may be saturated alkyl, saturated cycloalkyl, aryl, alkaryl, aralkyl and aralkaryl, each of up to 18 carbons, and nitrile mono-substituted derivatives of these.

B. CARBONYLATION position of the group consisting of hydrogen, water and alcohols. Except for the reactants, all three of these reactions employ essentially the conditions of the hydrogenations noted above.

Hydroformylation is conducted by heating a mixture of carbon monoxide, hydrogen and any olefin in the presence of a catalytically effective amount of at least one of the metal halide-trihalostannate(ll) or -trihalogermanate(ll) dispersions at a temperature of at least the melting point temperature of said dispersion. The process of hydroformylation may be particularly expressed by the equation:

wherein R R, R and R are defined as above.

Carboxylation is conducted by heating a mixture of carbon monoxide, water and any olefin in the presence of a catalytically effective amount of a catalyst as defined above for hydroformylation. This process may be particularly expressed by the equation:

wherein R R, R and R are defined as above.

Alkoxycarbonylation is conducted by heating a mixture of carbon monoxide, a monoor dihydric aliphatic alcohol and any olefin in the presence of a catalytically effective amount of a catalyst as defined above for hydroformylation. This process may be particularly expressed by the equation(s):

or, with a dihydric alcohol,

R being an alkyl or alkylene group of 6 or fewer carbons and the other Rs being as before.

C. PRODUCTS The hydrogenated, isomerized or carbonylated products are, in general, known chemicals. They can be isolated by known methods, e.g., by distillation of the reaction mixture. Alternatively, the crude reaction mixture can be isolated by first washing with water followed by separating of the hydrocarbon layer from the water layer. Pure product is then obtained by distillatron.

The compounds produced by the hydrogenation and- /or isomerization of olefins are useful as solvents and as chemical intermediates, such as precursors of fiberforming polyamides. For example, 1,5,9- cyclododecatriene can be hydrogenated to cyclododecene which can be oxidized with dilute potassium permanganate to dodecanedioic acid. Dodecanedioic acid reacts with diamines such as hexamethylenediamine to form a salt which can be heated under vacuum at a temperature of about 200C. to form a fiber-forming polyamide. Fibers can be prepared from the polyamide by melt spinning.

The amines produced by the hydrogenation of nitriles are useful in the preparation of dyestuffs and as dispersing agents as shown for ethylamine; Turner, The Condensed Chemical Dictionary," Reinhold Publications, New York, 1950, p. 271. The amines obtained are all primary amines and are also useful as acid scavengers.

The aldehydes produced in the carbonylation process are useful as solvents and as commercially important intermediates. For example, propionaldehyde is used in the production of polyvinyl acetals which are useful as adhesives and for the production of rubber chemicals. Turner, The Condensed Chemical Dictionary, Reinhold Publications, New York, 1950, p. 547.

The acids produced by the carbonylation of olefins in the presence of water are all useful for preparing the corresponding esters by reaction with alcohols. Esters, whether obtained from acids or by carbonylation of olefins in the presence of an alcohol, are useful as solvents and as plasticizers. bower molecular weight esters, particularly those containing up to 10 carbon atoms, are useful as solvents and diluents in paints and varnishes. Higher molecular weight esters, particularly those containing 8 carbon atoms and more, are useful 6 as plasticizers for polymers such as polyvinyl chloride, polymethyl methacrylate and polystyrene.

EMBODIMENTS OF THE INVENTION The following examples, in which parts and percentages are by weight, illustrate the catalytic activity of the dispersions of the metal salts in tetraalkylammonium trihalostannate(ll) and trihalogermanatefll) salts in the processes of the invention.

The preparation of the catalyst dispersions or solutions is in general obvious and described above. Examples l to 8 involve a procedure sometimes preferred for convenience. In this procedure, component A was first dissolved or dispersed in molten component B. The melt was then filtered to remove any undissolved or undispersed component A and the product allowed to solidify by cooling. It was then crushed so that the indicated amount of catalyst could be weighed out. In each example, the temperature specified for carrying out the reaction was high enough to insure that the previously prepared catalyst was molten during the process.

A. HY DROGENATION AND ISOMERIZATION Example 1 Hydrogenation of Methyl Linoleate A misture of 5.0 ml of methyl linoleate and 50 g of a 1 percent solution of platinum dichloride prepared in molten tetraethylammonium trichlorostannatefll) was agitated at 150C for 6 hours in a -ml stainless steel tube under a hydrogen pressure of atmospheres. The solid residue from the reaction vessel was distilled directly at 200C at 0.2 mm to give 3 ml of a cloudy liquid. The liquid was redistilled to give 2.0 g of a clear, colorless liquid, n 1.4522. (The refractive index is that expected for methyl oleate or one of its positional isomers.) The gas chromatogram of the product showed 62.8 area percent of a peak assignable to methyl oleate and 15.4 area percent of a peak assignable to an isomeric monoolefin.

When the unsaturated compounds shown in Table I are substituted for methyl linoleate in the hydrogenation procedures of Example 1, the compounds shown as hydrogenation products are the principal products obtained. It may be noted that with the unsaturated compounds of Example 1 and Table II, the formula becomes TABLE I 1 Item Olefin Hydrogenation Product(s) Ethyl S-octcnoate Amyl undecylenate Methyl sorbatc Ethyl octoate Amyl undecanoate Methyl 2-hexenoate and methyl hexanoate Propyl oleate and propyl LAN- 4 Propyl linoleate TABLE I-Continued Item Olefin Hydrogenation Product(s) octadecunoatc 5 Methyl acrylate Methyl propionutc 6 Ethyl-Z-nonenoate Ethyl nonanoate 7 Ethyl vinyl ketone Diethyl ketone 8 lsopropenyl methyl ketone lsopropyl methyl ketone Example 2 Hydrogenation of a Nitrile A mixture of 5.0 ml of acetonitrile and a solution of Y 0.5 g of platinum dichloride prepared in molten tetraethylammonium trichlorostannatefll) was agitated at ISOC. for 8 hours in an 80-ml stainless steel tube under a hydrogen pressure of 100 atmospheres. The crude reaction product was extracted with benzene. Gas chromatographic analysis of the extract showed the presence of ethylamine in addition to unchanged acetonitrile.

The following Examples were carried out as described in Example 25 Example Metal Halide Temp/Pres. Result When the nitriles shown in Table ll are substituted for acetonitrile in the procedures of Examples 2-4, the indicated amines are the principal products obtained.

TABLE ll ltem Nitrile Amine l Acetnnitrilc Ethylumine 2 Propinnitrile Propylamine. 3 lsohutymnitrilc lsohutylnmine 4 Lnuronitrile Laurylumine 5 Stearonitrile Stearylnminc 6 Cyclop ropanecurbonitrilc (Cyclopropylmethyl laminc 7 C yclopentanecnrbonitrilc (Cyclopentylmcthyl )umine 8 C yclohexanecnrbonitrile C yclohexylmethyl lamine 9 Dic'yclopcntylucctnnitrilc 2.2-Dicyclopcnlylethyl) amine l Benmnitrile Benzylnmine l l p-Tolunitrile p-Mcthylhenzyluminc l2 l-Phcnylcyclopropanecurl-Phcnylcyelopropylhunitrile methyllamine l3 a-Nuphthonitrilc a-Nnphthylmethylaminc 14 l -Phenunthrcnecarhonitrile l-Phenanthrylmethylumine l Bfifi-Triphehylpropio- 3.3.B-Triphenylpropylnitrile Y amine l6 Malononitrile l.3-Propylenediamine l7 Succinonitrile L-l-Butylenediamine l8 Adiponitrilc Hcxamethylenediumine l9 Phthulonitrile o-Xylylenc-md-diuminc Sehuconitrile Deeamethylcncdiamine nitrile B. CARBONYLATION Example 5 Hydroformylation of Ethylene A dispersion of 0.6 g of platinum dichloride prepared in 51, g of molten tetraethylammonium trichlorostannate(ll) was placed in a glass-lined 400 ml pressure vessel. The vessel was pressured to 1,000 atm. with a l :2: l0 mixture of hydrogen, ethylene, and carbonmonoxide and was agitated at C. for 6 hours. The volatile products were fractionated by vacuum distillation. I

Example 6 A dispersion of 0.5 g. of Na RhCl prepared in 39.3 g of molten tetraethylammonium trichlorostannatefll) was heated in a glass-lined pressure vessel at 90C for 6 hours under a pressure of 1,000 atm. of a 1:2: 10 mixture of hydrogen, ethylene, and carbon monoxide. Vacuum distillation of the volatile products showed the presence of propionaldehyde which was identified by its infrared spectrum and gas chromatography.

When the olefins shown in Table III are substituted for ethylene in the procedures of Examples 5 and 6, the compounds shown as aldehyde products are among the principal products obtained.

TABLE 111 Item Olefin Aldehyde(s) l Z-Butene Z-Methylbutyraldehyde 2 l-Octene Nonanal and Z-methyloctanal 3 l-Tetradccene Pentadecanal and Z-methyltetradecanal 4 LS-Hexadienc 6-Hcptenal and Z-methyl-S-hcxenal 5 LI l-Dodecudiene lZ-Tridecenal and Z-methyl-l ldodecenal 6 l.l3-Tctradccadienc l4-Pcntadecenal and Z-methyll 3-tetradecenal 7 Styrene 2-Phenylpropionaldehydc and 3-phenylpropionaldehyde 8 Stilbene 2,3-Diphenylpropionaldehyde 9 a-Vinylnaphthalenc Z-(cI-Naphthyl )propionaldehyde and 3-(a-nuphthyl)propionaldehyde l0 4-Phcnyl-l-hutene S-Phenylpentanal and 2-methyl-4-phenylbutanal' ll 3-Phenylcyclohutylethylene Z-Durylpropronal and 3-duryl-propional and 2-( J-phenylcyclobutyl )-propional 2.3.5 .G-Tetrumethylstyrcnc l 3 4.4-Dimethylstilhene 2.3Di(p-tolyl)propional l4 S-Phenylpipcrylene 6-Phenyl-3-hexenal and 4-phcnyl-2-vinylbutanal l5 S-p-Tolylpiperylenc 6-(p-Tolyl )-3-hexenal and 4-(p-tolyll-Z-vinylbutanal l6 Ethyl 6-octenoate Ethyl 7-fom1yloctanoate and ethyl 6-formyloctanoate l7 Amyl undecylenate Amyl ll-formylundecanoate and amyl lO-formylundecanoate l8 Methyl sorhute Methyl S-formyl-Z-hexenoate and methyl 3-forn1yl-4-hexenoate l9 Propyl linolcute Propyl l3-formyloleate and propyl l2-formyloleate 20 Methyl acrylate Methyl 3-formylpropionate 2| Ethyl 2-nonenoate Ethyl vinyl ketone lsnpropenyl methyl ketone Ethyl 3-formylnonanoate d-Oxohexanal 3-Mcthyl-4-oxopentanal Example 7 Carboxylation of l-Hexene A mixture of 5.0 g of l-hexene, 1.4 ml of water and 25 g of a 1 percent of platinum dichloride in tetraethyl- 3-(S-Phenylcyclobutyl)propional ammonium trichlorostannate(ll) was shaken at 90C for 6 hours under 400 atmospheres carbon monoxide pressure in a 80-ml stainless steel tube. The gases were vented. The residual solid was crushed and extracted with ether. Evaporation of the ether extract gave ca. 2 ml of a mixture of heptanoic acid and 2- methylhexanoie acid in a ratio of about 3:1 as determined by esterification and gas chromatographic analysis.

When the olefins shown in Table IV are substituted for l-hexene in the procedure of Example 7, the indicated acid products are the principal products obtained.

TABLE IV Item Olefin Acid(s) l Cyclohexene Cyclohexanccarhoxylic acid 2 l-Octene Nonanoie acid and Z-methyloctanoic acid 3 Propylene Butyric acid and isohutyric acid 4 lsohutylene lsovaleric acid and pivalic acid 5 Ethylene Propionic acid 6 lTctradecene Pcntadecanoic acid and 2methyltetradccanoic acid 7 l.l 3-Tetradccadiene l4-Pcntadecenoic acid and Z-methyll J-tetradecenoic acid 8 Styrene 3-Phenylpropionic acid and Z-phenylpropionic acid 9 Stilhene 2.3Diphcnylpropionic acid a-Vinylnaphthalene 3-(a-Naphthyl)propionic acid and 2 (a-naphthyl )propionic acid 5Phenyl\'aleric acid and 2methyl-4-phenylhutyrie acid 3-(3-Phenylcyclohutyl)propionic acid and 2-( 3-phenylcyelohutyl propionic acid Z-Durylpropionic acid and 3-durylpropionic acid 2.3-Di(p-tolyl )propionic acid o-Phenyli-hexenoic acid and 4-phenyl-l-vinylhutyric acid 6-( p-Tolyl )-4-hexenoic acid and 4-( p-tolyl )-2-vinylbutyric acid lM'ethyloctanedioic acid. monoethyl ester; and Z-ethylheptanedioic acid. munocthyl ester Dodecanedioic acid. monoamyl ester: and Z-methylundecanedioic acid. munoamyl ester 5-Methyl-2-hexencdioic acid. monomethyl ester: and Z-propenylsuccinic acid, mono'methyl ester Z-Pentyl-5-tetradecenedioie acid. monopropyl ester: and Z-hexyl-4-tridecenedioic acid. monopropyl ester Suceinie acid. monomethyl ester E-Hexylsuceinie acid. monoethyl ester 4-Oxohexanolc acid 3-Methyl-4-oxovaleric acid 4-Phenyl-l-hutene l2 3-Phenylcyclohutylethylene 2.35.o l'etraniethy[styrene 4.4'-Dimethylstilhcne 5-Phenylpiperylene 5 p-Tolylpiperylene Ethyl b-octenoate Amyl undecylenate Methyl sorhatc Propyl linoleate Zl Methyl acrylate Ethyl Z-nonenoate Ethyl vinyl ketone lsopropenyl methyl ketone Example 8 Alkoxycarbonylation of l-Hexene A mixture of 8.4 g of l-hexene, 4.8 g of methanol, and 45 g of a 1 percent solution of platinum dichloride prepared in molten tetraethylammonium trichlorostannate(ll) was agitated at 90C for 6 hours in a 400-ml glass-lined shaker tube under a carbon monoxide pressure of 450 atmospheres. Gas chromatographic analysis of the undistilled liquid product showed an approximate percent yield of a mixture of methyl heptano- TABLE V ltem Alcohol Olefin Ester( s) l Methanol Cyclohexene Methyl cyclohexanecarboxylate Ethyl nonanoate and ethyl 2-methyloctanoate Propyl butyrate and propyl isobutyrate Butyl isovalerate and butyl pivalate lsobutyl isovalerate and isobutyl pivalate tert-Butyl valerate and tert-butyl Z-methylbutyrate Pentyl butyrate and pentyl isobutyrate Hexyl heptanoate and hexyl Z-methylhexanoate Ethylene propionate Methylethylene butyrate and methylethylene isobutyrate 1,4-Butylene propionate LS-Pentamcthylene valerate. LS-pentamethylene Z-methyl-butyrate and 1,5-pentamethylene Z-methylbutyrate valerate 3-Propyltrimethylene butyrate. 3-propyltrimethylene isobutyrate and 3-propyltrimethylene butyrate isobutyrate Lfi-Hexamethylene propionate Dicthyl succinate Dimethyl dodecanedioate and dimethyl Z-methyIundecanedioate Methyl pentadecanoate and methyl Z-methyltetradecanoate Methyl l4-pentadeccnoate and methyl 2-methyll 3- tetradecenoate Ethyl Z-phenylpropionate and ethyl 3-phenylpropionate Ethyl 2 Ethanol l-Octene 3 Propanol Propylene 4 Butanol Isobutylene 5 lsobutanol lsobutylene 6 tert-butanol l-Butene 7 Pentanol Propylene 8 Hexanol l-Hexene 9 Ethylene glycol l.2-Propylene glycol Ethylene Propylene l,4-Butanediol l2 l.5-Pentanediol Ethylene l-Butene l.3Hexanediol Propylene l4 l,6-Hexanediol Ethylene Ethanol Methanol Ethyl acrylatc Methyl undecylenate Methanol l-Tetradeeene Methanol l.l3-

Tetradecadiene Ethanol Styrene 2 l Methanol a-Vinylnaphthalene Methanol 4-Phenyl-l' butene 3. Phenylcyclobutylethylene Methanol Ethanol 2.3.5 .6-tetramethylstyrene Methanol 4,4-

Dimethylstilbene 29 Amyl alcohol TABLE V-Contmued item Alcohol Olefin Ester(s) 26 Ethanol 5- Ethyl Phenylpipcry- 6-phenyl-4-hexenoatc lene and ethyl 4-phenyl-2- vinylbutanoatc 27 Ethanol 5-p Ethyl Tolylpipcrylene 6( p-tolyl )-4-hexenoate and ethyl 4-(p-tolyl)-Z- vinylbutanoatc 28 Ethanol Ethyl Diethyl 6octenoate Z-methyloctancdioate and diethyl Z-ethylheptanedioatc Diamyl dodecancdioate and diamyl 2-mcthylundeeanedioatc 3O Methanol Methyl sorhatc Dimcthyl S-rnethyl-Z- hexcncdioatc and dimethyl 2-propcnylsuccinatc 3i Propanol Propyl linoleatc Dipropyl l-pcntyl-5-tctradccenetlioatc and dipropyl 2-hcxyl-4-tridecencdioate 32 Methanol Methyl acrylatc Dimethyl succinatc 33 Ethanol Ethyl Diethyl 2hexylsuccinate 2-noncnoate 34 Methanol Ethyl vinyl Methyl 4-oxohexanoatc ketone 35 Methanol lsopropcnyl Methyl methyl ketone 3-methyl-4-oxovalerate Since obvious modifications and equivalents will be evident to those skilled in the chemical ans, I propose to be bound solely by the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

l. A process for the carbonylation of an olefin of the formula wherein R, R, R and R, individually, are hydrogen, alkyl of up to 12 carbons, alkenyl of up to 12 carbons. aryl of up to 10 carbons, aralkyl of up to 10 carbons, alkaryl of up to 10 carbons, aralkenyl of up to l carbons, alkoxycarbonylalkyl of up to 14 carbons, alkoxycarbonylalkenyl of up to 14 carbons, -COOR or -COR where R is lower alkyl; or R and R conjointly is alkylene or alkenylene of 4 to 6 carbons; or R and R is alkylene or alkenylene of up to carbons or the divalent radical of the formula:

+CH CH =CH+CH CH =CH+CH with the proviso that at least two of R R, R and R are hydrogen,

which comprises reacting the olefin with carbon monoxide and an active-hydrogen-containing member of the group consisting of hydrogen, water and monoand dihydric alcohols of up to 6 carbons,

in the presence of a catalytic amount of a dispersion at a temperature between about 10 and 350C. and above its melting point, said dispersion consisting essentially of:

(A) at least 0.05 weight percent of a chloride, bromideor iodide-containing salt of a metal having an atomic number of 26-28, 44-46, or 76-78; and

(B) a molten salt of the formula [R R R R Q]YX wherein R R R and R independently, contain up to 18 carbons and are alkyl, cycloalkyl, aryl, alkaryl or aralkyl; or

R and R conjointly, contains 4 to 6 carbons and is alkylene; or

R, R R and Q conjointly is pyridinium or quinolinium;

Q is nitrogen or phosphorus;

Y is tin or germanium; and

X is chlorine or bromine.

2. The process of claim 1 wherein the olefin is reacted with hydrogen and carbon monoxide in the presence of platinum dichloride dispersed in tetraethylammonium trichlorostannate( ll 3. The process of claim 2 wherein the olefin is ethylene.

4. The process of claim 1 wherein the olefin is reacted with hydrogen and carbon monoxide in the presence of Na RhCl dispersed in tetraethylammonium trichlorostannate( ll 5. The process of claim 4 wherein the olefin is ethylene.

6. The process of claim 1 wherein the olefin is reacted with carbon monoxide and water in the presence of platinum dichloride dispersed in tetraethylammonium trichlorostannate( II 7. The process of claim 6 wherein the olefin is lhexene.

8. The process of claim 1 wherein the olefin is reacted with carbon monoxide and a monoor dihydric aliphatic alcohol of up to 6 carbons in the presence of platinum dichloride dispersed in tetraethylammonium trichlorostannate( ll 9. The process of claim 8 wherein the olefin is lhexene and the alcohol is methanol.

P614050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,832,591 Dated August 7, 97

Inventor) George W. Parshall It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 48, "Sn(II" should read "Sn(II)".

Column 6, line 27, "misture" should read "mixture".

Column 6, line 47, "II" should read "I".

Column 6, line 50, "R" should read "R Column 11, line 40, "R" should read "R 3ignec? and sealed this 1st day oi April 1'375.

(SEAL) Attest:

' C. I-L-KRSHALL DJI-Z RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks 

2. The process of claim 1 wherein the olefin is reacted with hydrogen and carbon monoxide in the presence of platinum dichloride dispersed in tetraethylammonium trichlorostannate(II).
 3. The process of claim 2 wherein the olefin is ethylene.
 4. The process of claim 1 wherein the olefin is reacted with hydrogen and carbon monoxide in the presence of Na3RhCl6 dispersed in tetraethylammonium trichlorostannate(II).
 5. The process of claim 4 wherein the olefin is ethylene.
 6. The process of claim 1 wherein the olefin is reacted with carbon monoxide and water in the presence of platinum dichloride dispersed in tetraethylammonium trichlorostannate(II).
 7. The process of claim 6 wherein the olefin is 1-hexene.
 8. The process of claim 1 wherein the olefin is reacted with carbon monoxide and a mono- or dihydric aliphatic alcohol of up to 6 carbons in the presence of platinum dichloride dispersed in tetraethylammonium trichlorostannate(II).
 9. The process of claim 8 wherein the olefin is 1-hexene and the alcohol is methanol. 